US9657116B2 - Process of polyolefin functionalization - Google Patents

Process of polyolefin functionalization Download PDF

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US9657116B2
US9657116B2 US14/900,989 US201414900989A US9657116B2 US 9657116 B2 US9657116 B2 US 9657116B2 US 201414900989 A US201414900989 A US 201414900989A US 9657116 B2 US9657116 B2 US 9657116B2
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polyolefin
mixture
alkyls
vinyl
unsaturated carbonyl
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Man Kit Ng
David T. Ferrughelli
Hong Cheng
Emmanuel Ulysse
Donna J. Crowther
Edward A. Lemon, Jr.
Patrick Brant
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • C08F110/10—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains

Definitions

  • the present invention relates in general to a method to modify vinyl terminated polyolefins, and in particular, improving the functionalization of vinyl terminated polyolefins with ⁇ , ⁇ -unsaturated carbonyl compounds and the resulting functionalized polymers.
  • the inventors have found that the thermal functionalization, especially maleation reaction, of vinyl terminated propylene-based homopolymer (and copolymer of propylene with higher alpha olefins such as 1-butene and 1-hexene) exhibits slower kinetics than that of vinylidene-terminated polyisobutylene of comparable number average molecular weights (Mn) in the range of about 500 to 3000 g/mol.
  • Mn number average molecular weights
  • commercial highly reactive PIB Mn 750 g/mol, vinylidene terminated, about 83-87%) undergoes maleation in the presence of 1.6 equivalent of maleic anhydride (MA) at 190° C.
  • PIB-SA material under about 1 atmospheric pressure (glassware conditions) for about 2 hours to afford a PIB-SA material with about 1.11 succinic anhydride functionality per polymer chain (e.g., see Example 1 below).
  • aPP vinyl-terminated atactic polypropylene
  • Mn about 1000 g/mol only gave a PP-SA material with less than 0.21 succinic anhydride functionality per polymer after 2 hours at 200° C. at about 120-140 psi of nitrogen when 2 equivalents of MA was used in autoclave (see, for example, Example 6 below). Consequently, long reaction times (between 30 to 80 hours) and/or large excess maleic anhydride are typically needed for achieving high conversion of the vinyl at temperature of 190° C. or below.
  • the invention disclosed herein is directed to a method of functionalizing a vinyl terminated polyolefin, an unexpectedly slow and inefficient reaction, the method comprising combining (meaning, as one of skill in the art would understand, contacting under conditions sufficient to effect a desired chemical reaction, or “reacting”) a vinyl terminated polyolefin and a ⁇ , ⁇ -unsaturated carbonyl compound at a temperature of at least 150° C. but as high as 250° C. or more, and a pressure of at least 14 psi, but as high as 200 or 300 psi or more, thereby forming a functionalized polyolefin.
  • the functionalized polyolefin comprises a compound or mixture of compounds represented by one or more of the following formulae:
  • each R 1 is, independently, selected from hydrogen and C 1 to C 4 or C 10 alkyls; n is an integer from 2 or 20 to 500 or 800; and each X is, independently, a functional group derived from the ⁇ , ⁇ -unsaturated carbonyl compound.
  • the inventors have found an improved methodology of functionalizing vinyl terminated polyolefins with ⁇ , ⁇ -unsaturated carbonyl compounds. By raising the reaction temperature, reaction pressure, or both, the overall yield and rate of reaction improves and the reaction time to get a high rate of functionalization decreases.
  • VTPs vinyl terminated polyolefins
  • MWD a MWD from 1.0 to 1.5 for atactic propylene oligomer distilled fractions
  • backbone molecular composition C 2 only, C 3 only, C 3 C 2 , C 3 C 4 , C 3 C 5 , C 3 C 6 , C 3 C 8 , C 3 C 10 , etc.
  • ⁇ , ⁇ -unsaturated carbonyl functionalization is maleation of atactic polypropylene bottoms (residual liquid from distillation of low Mn aPP oligomer sample) such as demonstrated herein (e.g., example 10).
  • the invention is directed to efficient functionalization of VTPs with one or multiple ⁇ , ⁇ -unsaturated carbonyl compounds, or anhydride groups by maleation (also known as Alder-ene reaction), of terminal C ⁇ C bond, and derivatization of the resulting anhydride functionalities.
  • maleation also known as Alder-ene reaction
  • n is an integer from 2 to 800
  • DETA diethylenetriamine
  • TETA triethylenetetramine
  • TEPA tetraethylenepentamine
  • PEHA pentaethylenehexamine
  • hexaethyleneheptamine polyethyleneamine heavy bottoms.
  • nucleophilic reagents can also be used, including, for example, monoamines, diamines, amino alcohols, polyetheramines, JeffamineTM, polyols (e.g., pentaerythritol), polyalkylene glycols (PAG), polyalkylene polyamine, and the like.
  • the polyolefin anhydride itself may be used to prepare the corresponding succinic acid and the corresponding alkali/alkaline salts for application such as surfactants.
  • the functionalized derivatives may also find extensive uses as dispersants in lubricating oils, antifoulant dispersants for heavy hydrocarbon refinery streams, as well as dispersants for polar inorganic and organic particulates, just to name a few.
  • VTP Vinyl-Terminated Polyolefin
  • the vinyl terminated polyolefins useful in the inventive method of functionalizing a vinyl terminated polyolefin with one or more ⁇ , ⁇ -unsaturated carbonyl compounds can be made in any number of ways.
  • the VTP's useful herein are polymers as first described in US 2009-0318644 (referred to therein as vinyl terminated “macromers” or “macromonomers”) having at least one terminus (CH 2 CH—CH 2 -oligomer or polymer) represented by formula (I):
  • allyl chain ends are represented by the formula (II):
  • the amount of allyl chain ends is determined using 1 H NMR at 120° C. using deuterated tetrachloroethane as the solvent on a 500 MHz machine, and in selected cases confirmed by 13 C NMR. These groups (I) and (II) will react to form a chemical bond with a metal, as mentioned above, to form the M-CH 2 CH 2 -polymer. In any case, Resconi has reported proton and carbon assignments (neat perdeuterated tetrachloroethane used for proton spectra while a 50:50 mixture of normal and perdeuterated tetrachloroethane was used for carbon spectra; all spectra were recorded at 100° C.
  • the vinyl-terminated propylene-based polymers may also contain an isobutyl chain end.
  • “Isobutyl chain end” is defined to be an oligomer having at least one terminus represented by the formula (III):
  • the isobutyl chain end is represented by one of the following formulae (IV):
  • the percentage of isobutyl end groups is determined using 13 C NMR (as described in the example section) and the chemical shift assignments in Resconi for 100% propylene oligomers.
  • the vinyl-terminated polymers described herein have an allylic terminus, and at the opposite end of the polymer an isobutyl terminus.
  • the VTPs can be made by any suitable means, but most preferably the VTPs are made using conventional slurry or solution polymerization processes using a combination of bridged metallocene catalyst compounds (especially bridged bis-indenyl or bridged 4-substituted bis-indenyl metallocenes) with a high-molecular volume (at least a total volume of 1000 ⁇ 3 ) perfluorinated boron activator, for example as described in US 2012-0245299.
  • bridged metallocene catalyst compounds especially bridged bis-indenyl or bridged 4-substituted bis-indenyl metallocenes
  • a high-molecular volume at least a total volume of 1000 ⁇ 3
  • perfluorinated boron activator for example as described in US 2012-0245299.
  • the vinyl terminated polyolefin can be any polyolefin having a vinyl-terminal group, and is preferably selected from the group consisting of vinyl-terminated isotactic polypropylenes, atactic polypropylenes, syndiotactic polypropylenes, propylene-butene copolymers, propylene-hexene copolymers, and propylene-ethylene copolymers (wherein the copolymers may be random, elastomeric, impact and/or block), and combinations thereof, each having a number average molecular weight (Mn) of at least 300 g/mole.
  • Mn number average molecular weight
  • greater than 90 or 94 or 96% of the polyolefin comprises terminal vinyl groups; or within the range of from 50 or 60 wt % to 70 or 80 or 90 or 95 or 98 or 99%.
  • the vinyl terminated polyolefins preferably have a Mn value of at least 200 or 400 or 1000 or 5000 or 20,000 g/mole, or within the range of from 200 or 400 or 500 g/mole to 20,000 or 30,000 or 40,000 or 50,000 or 100,000 or 200,000 or 300,000 g/mole.
  • the vinyl terminated polyolefins preferably have a weight average molecular weight (Mw) value of at least 500 or 800 or 1000 or 5000 or 20,000 g/mole, or within the range of from 500 or 800 or 1000 or 2000 g/mole to 6,000 or 10,000 or 12,000 or 20,000 or 30,000 or 40,000 or 50,000 or 100,000 or 200,000 or 300,000 g/mole.
  • Mw weight average molecular weight
  • the VTP useful herein is amorphous polypropylene, and desirably has a glass transition temperature (Tg) of less than 10 or 5 or 0° C., more preferably less than ⁇ 10° C.; or within the range of from 0 or ⁇ 5 or ⁇ 10° C.
  • the VTPs are preferably linear, meaning that there is no polymeric or oligomeric branching from the polymer backbone, or described quantitatively, having a branching index “g” (or g′ (vis avg) ) of at least 0.90 or 0.96 or 0.97 or 0.98, wherein the “branching index” is well known in the art and measurable by published means, and the value of such branching index referred to herein is within 10 or 20% of the value as measured by any common method of measuring the branching index for polyolefins as is known in the art such as in US 2013-0090433.
  • VTP is one wherein the vinyl terminated polyolefin is a compound or mixture of compounds represented by the formula (V):
  • each R is selected from hydrogen and C 1 to C 4 or C 10 alkyls; and n is an integer from 2 or 4 or 10 or 20 to 50 or 100 or 200 or 500 or 800.
  • a method of functionalizing a vinyl terminated polyolefin comprising, or consisting essentially of, combining a VTP and a ⁇ , ⁇ -unsaturated carbonyl compound at a temperature of at least 150 or 160 or 180 or 200 or 220 or 240 or 250° C. and a pressure of at least 14 or 20 or 50 or 100 or 200 or 300 or 400 psi, forming a functionalized polyolefin. More preferably, the reaction is conducted at a temperature within the range of from 190 or 200 or 220° C. to 260 or 280 or 300 or 320° C.
  • the preferred pressure range may be within the range from 80 or 100 or 120 psi to 300 or 350 or 400 or 500 psi.
  • Consisting essentially of what is meant is that no other major reactants are present to effect the identity of the final functionalized polyolefin product to no more than 3 wt % of the total product.
  • ⁇ , ⁇ -unsaturated carbonyl compound is an unsaturated anhydride. Even more preferably, the ⁇ , ⁇ -unsaturated carbonyl compound is a compound or mixture of compounds represented by one or more of the formulae (VI):
  • each R is, independently, a hydrogen or a C 1 to C 10 or C 20 alkyls (linear or branched), or mixture thereof.
  • the ⁇ , ⁇ -unsaturated carbonyl compound is maleic anhydride or a C 1 to C 5 alkyl substituted version thereof, the structures not being limited to the cis- or trans-isomers thereof.
  • the combining takes place using neat carbonyl compound and/or VTP, where the VTP may be molten if not a liquid at the desired reaction temperature.
  • the carbonyl compound and VTP can be mixed with or without added solvent. Regardless, the carbonyl compound and VTP are mixed for a period within the range from a few minutes or 10 minutes or 30 minutes or 1 hour or 2 hours or 3 hours to 4 or 6 or 8 or 10 or 16 or 24 hours.
  • from 0.8 or 1.0 to 1.5 or 2.0 or 3.0 or 4.0 or 5.0 or 6.0 equivalents of the ⁇ , ⁇ -unsaturated carbonyl compound are added per equivalent of VTP.
  • the combining preferably takes place in an inert atmosphere such as under nitrogen, most preferably to the exclusion of oxygen and/or water vapor.
  • the combining takes place such that the resulting product of the combining, the functionalized polyolefin, has at least 0.3 or 0.5 or 0.6 or 0.8 or 0.9 or 1.0 or 1.1 functional groups per polyolefin chain; or within a range of from 0.3 or 0.5 or 0.8 or 0.9 to 1.3 or 1.4 or 1.6 or 1.8 or 2.0 or 2.5 or 3.0 functional groups per polyolefin chain.
  • Lewis Acids selected from the group consisting of titanium halides, titanium alkyls and alkoxys, tin halides, tin alkyls and alkoxys, aluminum halides, aluminum alkyls and alkoxys, boron halides, boron alkyls and alkoxys, zinc halides, and combinations thereof; preferably, wherein the Lewis Acid is selected from the group consisting of SnCl 4 , AlCl 3 , Me 2 AlCl, EtAlCl 2 , Et 2 AlCl, TiCl 4 , TiCl 2 (i-PrO) 2 , TiBr 2 (i-PrO) 2 , BF 3 and mixtures thereof (where “Me” is methyl, “Et” is ethyl, and “i-Pr” is isopropyl).
  • the temperature of combining is desirably lowered
  • inventive functionalized polyolefin is preferably a compound or mixture of compounds represented by one or more of the formulae (VII):
  • each R 1 is, independently, selected from hydrogen or C 1 to C 4 or C 10 alkyls; n is an integer from 2 or 4 or 10 or 20 or 50 or 100 or 200 or 500 or 800; and each X is, independently, a functional group derived from the ⁇ , ⁇ -unsaturated carbonyl compound.
  • the most preferred functionalized polyolefin is a mono- or bis-succinic anhydride, or mixture thereof.
  • the inventive functionalized polyolefin may be made by the inventive method described herein or any other desirable method.
  • the functionalized polyolefin may have any number of uses, such as fouling inhibitors or mitigators, or as additives in lubricant oils, or as additives in rubber/elastomeric compositions such as in tire treads to compatabilize the components therein.
  • Mn was determined using the GPC-DRI method described below.
  • Mn, Mw, and Mz may be measured by using a Gel Permeation Chromatography (GPC) method using a High Temperature Size Exclusion Chromatograph (SEC, either from Waters Corporation or Polymer Laboratories), equipped with a differential refractive index detector (DRI).
  • Molecular weight distribution (MWD) is Mw (GPC)/Mn (GPC).
  • the nominal flow rate is 0.5 cm 3 /min and the nominal injection volume is 300 ⁇ L.
  • the various transfer lines, columns and differential refractometer (the DRI detector) are contained in an oven maintained at 135° C.
  • Solvent for the SEC experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4 trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 ⁇ m glass pre-filter and subsequently through a 0.1 ⁇ m Teflon filter. The TCB is then degassed with an online degasser before entering the SEC.
  • Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160° C. with continuous agitation for about 2 hours. All quantities are measured gravimetrically.
  • the TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/mL at 25° C. and 1.324 g/mL at 135° C.
  • the injection concentration is from 1.0 to 2.0 mg/mL, with lower concentrations being used for higher molecular weight samples.
  • the DRI detector and the injector Prior to running each sample the DRI detector and the injector are purged. Flow rate in the apparatus is then increased to 0.5 mL/minute, and the DRI is allowed to stabilize for 8 to 9 hours before injecting the first sample.
  • (dn/dc) 0.104 for propylene polymers and ethylene polymers, and 0.1 otherwise.
  • concentration is expressed in g/cm 3
  • molecular weight is expressed in g/mol
  • intrinsic viscosity is expressed in dL/g.
  • a functionalized polyolefin comprising a compound or mixture of compounds represented by one or more of the following formulae:
  • each R 1 is, independently, selected from hydrogen or C 1 to C 4 or C 10 alkyls; n is an integer from 2 or 4 or 10 or 20 to 50 or 100 or 200 or 500 or 800; and each X is, independently, a functional group derived from the ⁇ , ⁇ -unsaturated carbonyl compound.
  • P2. A method of functionalizing a vinyl terminated polyolefin, the method comprising (or consisting essentially of) combining a vinyl terminated polyolefin and a ⁇ , ⁇ -unsaturated carbonyl compound at a temperature of at least 150 or 160 or 180 or 200 or 220 or 240 or 250° C.
  • each R is, independently, a hydrogen, a C 1 to C 10 or C 20 alkyls (linear or branched), or mixture thereof; preferably, the ⁇ , ⁇ -unsaturated carbonyl compound is maleic anhydride, the structures not being limited to the cis- or trans-isomers thereof.
  • P5. The method of any one of the previous numbered paragraphs, wherein the vinyl terminated polyolefin is compound or mixture of compounds represented the formula:
  • R is selected from hydrogen and C 1 to C 4 or C 10 alkyls; and n is an integer from 2 or 4 or 10 or 20 to 50 or 100 or 200 or 500 or 800.
  • Mn number average molecular weight
  • the functionalized polyolefin has at least 0.3 or 0.5 or 0.6 or 0.8 or 0.9 or 1.0 or 1.1 functional groups per polyolefin chain; or within a range of from 0.3 or 0.5 or 0.8 or 0.9 to 1.3 or 1.4 or 1.6 or 1.8 or 2.0 or 2.5 or 3.0 functional groups per polyolefin chain.
  • the combining takes place in a period within the range from a few minutes or 10 minutes or 30 minutes or 1 hour or 2 hours or 3 hours to 4 or 6 or 8 or 10 or 16 or 24 hours.
  • a Lewis Acid selected from the group consisting of titanium halides, titanium alkyls and alkoxys, tin halides, tin alkyls and alkoxys, aluminum halides, aluminum alkyls and alkoxys, boron halides, boron alkyls and alkoxys, zinc halides, and combinations thereof; more preferably, wherein the Lewis Acid is selected from the group consisting of SnCl 4 , AlCl 3 , Me 2 AlCl, EtAlCl 2 , Et 2 AlCl, TiCl 4 , TiCl 2 (i-PrO) 2 , TiBr 2 (i-PrO) 2 , BF 3 and mixtures thereof (where “Me” is methyl, “Et” is ethyl, and “i-Pr” is isopropyl).
  • each R 1 is, independently, selected from hydrogen or C 1 to C 4 or C 10 alkyls; n is an integer from 2 or 4 or 10 or 20 or 50 or 100 or 200 or 500 or 800; and each X is, independently, a functional group derived from the ⁇ , ⁇ -unsaturated carbonyl compound.
  • P12 The method of any one of the previous numbered paragraphs, wherein the combining takes place in an inert atmosphere.
  • P13 The method of any one of the previous numbered paragraphs, wherein from 0.8 or 1.0 to 1.5 or 2.0 or 3.0 or 4.0 or 5.0 or 6.0 equivalents of the ⁇ , ⁇ -unsaturated carbonyl compound are added per equivalent of VTP.
  • a functionalized polyolefin made by the method of any one of the previous numbered paragraphs.
  • a vinyl terminated polyolefin in a reaction with at least one ⁇ , ⁇ -unsaturated carbonyl compound as these components are described herein. Also described is the use of the inventive functionalized polyolefin as a fouling mitigator, or compatabilizer in elastomeric or lubricant compositions.

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Abstract

Disclosed is a method of functionalizing a vinyl terminated polyolefin, the method comprising combining a vinyl terminated polyolefin and a α,β-unsaturated carbonyl compound at a temperature of at least 150° C. and a pressure of at least 14 psi, forming a functionalized polyolefin. The functionalized polyolefin comprises a compound or mixture of compounds represented the formula:
Figure US09657116-20170523-C00001
wherein each R1 is, independently, selected from hydrogen and C1 to C4 or C10 alkyls; n is an integer from 2 to 800; and each X is, independently, a functional group derived from the α,β-unsaturated carbonyl compound.

Description

PRIORITY CLAIM TO RELATED APPLICATIONS
This present application is a National Stage Application of International Application No. PCT/US2014/044872, filed Jun. 30, 2014, which claims priority to U.S. Ser. No. 61/881,284 filed Sep. 23, 2013, both of which are incorporated by reference.
FIELD OF THE INVENTION
The present invention relates in general to a method to modify vinyl terminated polyolefins, and in particular, improving the functionalization of vinyl terminated polyolefins with α,β-unsaturated carbonyl compounds and the resulting functionalized polymers.
BACKGROUND
The inventors have found that the thermal functionalization, especially maleation reaction, of vinyl terminated propylene-based homopolymer (and copolymer of propylene with higher alpha olefins such as 1-butene and 1-hexene) exhibits slower kinetics than that of vinylidene-terminated polyisobutylene of comparable number average molecular weights (Mn) in the range of about 500 to 3000 g/mol. For example, commercial highly reactive PIB (Mn 750 g/mol, vinylidene terminated, about 83-87%) undergoes maleation in the presence of 1.6 equivalent of maleic anhydride (MA) at 190° C. under about 1 atmospheric pressure (glassware conditions) for about 2 hours to afford a PIB-SA material with about 1.11 succinic anhydride functionality per polymer chain (e.g., see Example 1 below). In comparison, vinyl-terminated atactic polypropylene (aPP) of Mn about 1000 g/mol only gave a PP-SA material with less than 0.21 succinic anhydride functionality per polymer after 2 hours at 200° C. at about 120-140 psi of nitrogen when 2 equivalents of MA was used in autoclave (see, for example, Example 6 below). Consequently, long reaction times (between 30 to 80 hours) and/or large excess maleic anhydride are typically needed for achieving high conversion of the vinyl at temperature of 190° C. or below.
It is not understood why the rate of maleation of vinyl-terminated PP is so inefficient and it is unexpected that it should be slow. The lower reactivity of the vinyl double bond versus the vinylidene double bond may be rationalized in terms of the relative reactivity steric hindrance of the allylic hydrogens when the six-membered-like cyclic transition state is adopted by the two reactants (three methyl hydrogens in vinylidene versus two internal methylene hydrogens in vinyl). A technological need therefore exists for identifying a practical method with conditions that would provide high degree of functionalization of vinyl double bond with anhydride group toward thermal “ene” reaction (with maleic anhydride or other olefinically unsaturated carboxylic acid derivatives).
Related disclosures include U.S. Ser. No. 13/804,727 filed Mar. 14, 2013; U.S. Ser. No. 13/804,507 filed Mar. 14, 2013; US 2010-0170829; US 2009-0318646; U.S. Pat. No. 7,183,359; R. Mülhaupt et al. “Novel Polypropylene Materials Derived from Vinylidene-terminated Oligopropenes” in 4 POLYMER FOR ADVANCED TECHNOLOGY pp. 439-449 (1993); R. Mülhaupt et al. “Reactive Blending of Polypropylene/Polyamide-6 in the Presence of Tailor made Succinic Anhydride-terminated Oligopropene Compatabilizers” in 4 POLYMER FOR ADVANCED TECHNOLOGY pp. 465-474 (1993); A. S. Sainath “Synthesis and Characteristics of Succinic Anhydride- and Disodium Succinate-Terminated Low Molecular Weight Polyethylenes”, 42(13) MACROMOLECULES 4356-4358 (2009); and M. Thompson et al. “Terminal Functionalization of Polypropylene via the Alder Ene Reaction”, in 39(2) POLYMER 327-334 (1998).
SUMMARY
The invention disclosed herein is directed to a method of functionalizing a vinyl terminated polyolefin, an unexpectedly slow and inefficient reaction, the method comprising combining (meaning, as one of skill in the art would understand, contacting under conditions sufficient to effect a desired chemical reaction, or “reacting”) a vinyl terminated polyolefin and a α,β-unsaturated carbonyl compound at a temperature of at least 150° C. but as high as 250° C. or more, and a pressure of at least 14 psi, but as high as 200 or 300 psi or more, thereby forming a functionalized polyolefin. Preferably, the functionalized polyolefin comprises a compound or mixture of compounds represented by one or more of the following formulae:
Figure US09657116-20170523-C00002
wherein each R1 is, independently, selected from hydrogen and C1 to C4 or C10 alkyls; n is an integer from 2 or 20 to 500 or 800; and each X is, independently, a functional group derived from the α,β-unsaturated carbonyl compound.
DETAILED DESCRIPTION
The inventors have found an improved methodology of functionalizing vinyl terminated polyolefins with α,β-unsaturated carbonyl compounds. By raising the reaction temperature, reaction pressure, or both, the overall yield and rate of reaction improves and the reaction time to get a high rate of functionalization decreases. The functionalization method disclosed can be applied to vinyl terminated polyolefins (or “VTPs”) with different molecular weight, molecular weight distribution (e.g., a MWD from 1.0 to 1.5 for atactic propylene oligomer distilled fractions) and backbone molecular composition (C2 only, C3 only, C3C2, C3C4, C3C5, C3C6, C3C8, C3C10, etc.) including crystallizable and amorphous substrates. An example of α,β-unsaturated carbonyl functionalization is maleation of atactic polypropylene bottoms (residual liquid from distillation of low Mn aPP oligomer sample) such as demonstrated herein (e.g., example 10). There, the aPP starting material has a low polydispersity (Mw/Mn) of 1.20, which on maleation, gave an anhydride functionalized material with Mw/Mn=1.27.
Thus, the invention is directed to efficient functionalization of VTPs with one or multiple α,β-unsaturated carbonyl compounds, or anhydride groups by maleation (also known as Alder-ene reaction), of terminal C═C bond, and derivatization of the resulting anhydride functionalities. A common scheme for such reactions is shown (where “x” is 0 or an integer from 1 to 10 or 20; “n” is an integer from 2 to 800):
Figure US09657116-20170523-C00003
The resulting anhydride functionalities can be used for reacting with nucleophilic reagents including polyethyleneamines with general molecular formula H2N(CH2CH2NH)xH (where x=1, 2, 3, . . . ) such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), hexaethyleneheptamine or polyethyleneamine heavy bottoms. Other types of nucleophilic reagents can also be used, including, for example, monoamines, diamines, amino alcohols, polyetheramines, Jeffamine™, polyols (e.g., pentaerythritol), polyalkylene glycols (PAG), polyalkylene polyamine, and the like. The polyolefin anhydride itself may be used to prepare the corresponding succinic acid and the corresponding alkali/alkaline salts for application such as surfactants. The functionalized derivatives may also find extensive uses as dispersants in lubricating oils, antifoulant dispersants for heavy hydrocarbon refinery streams, as well as dispersants for polar inorganic and organic particulates, just to name a few.
Vinyl-Terminated Polyolefin (VTP)
The vinyl terminated polyolefins useful in the inventive method of functionalizing a vinyl terminated polyolefin with one or more α,β-unsaturated carbonyl compounds can be made in any number of ways. Preferably, the VTP's useful herein are polymers as first described in US 2009-0318644 (referred to therein as vinyl terminated “macromers” or “macromonomers”) having at least one terminus (CH2CH—CH2-oligomer or polymer) represented by formula (I):
Figure US09657116-20170523-C00004
where the “
Figure US09657116-20170523-P00001
” represents the oligomer or polymer chain. Preferably, the allyl chain ends are represented by the formula (II):
Figure US09657116-20170523-C00005
The amount of allyl chain ends is determined using 1H NMR at 120° C. using deuterated tetrachloroethane as the solvent on a 500 MHz machine, and in selected cases confirmed by 13C NMR. These groups (I) and (II) will react to form a chemical bond with a metal, as mentioned above, to form the M-CH2CH2-polymer. In any case, Resconi has reported proton and carbon assignments (neat perdeuterated tetrachloroethane used for proton spectra while a 50:50 mixture of normal and perdeuterated tetrachloroethane was used for carbon spectra; all spectra were recorded at 100° C. on a Bruker AM 300 spectrometer operating at 300 MHz for proton and 75.43 MHz for carbon) for vinyl-terminated propylene polymers in Resconi et al, 114 J. AM. CHEM. Soc. pp. 1025-1032 (1992) that are useful herein.
The vinyl-terminated propylene-based polymers may also contain an isobutyl chain end. “Isobutyl chain end” is defined to be an oligomer having at least one terminus represented by the formula (III):
Figure US09657116-20170523-C00006
Preferably, the isobutyl chain end is represented by one of the following formulae (IV):
Figure US09657116-20170523-C00007
The percentage of isobutyl end groups is determined using 13C NMR (as described in the example section) and the chemical shift assignments in Resconi for 100% propylene oligomers. Preferably, the vinyl-terminated polymers described herein have an allylic terminus, and at the opposite end of the polymer an isobutyl terminus.
The VTPs can be made by any suitable means, but most preferably the VTPs are made using conventional slurry or solution polymerization processes using a combination of bridged metallocene catalyst compounds (especially bridged bis-indenyl or bridged 4-substituted bis-indenyl metallocenes) with a high-molecular volume (at least a total volume of 1000 Å3) perfluorinated boron activator, for example as described in US 2012-0245299.
The vinyl terminated polyolefin can be any polyolefin having a vinyl-terminal group, and is preferably selected from the group consisting of vinyl-terminated isotactic polypropylenes, atactic polypropylenes, syndiotactic polypropylenes, propylene-butene copolymers, propylene-hexene copolymers, and propylene-ethylene copolymers (wherein the copolymers may be random, elastomeric, impact and/or block), and combinations thereof, each having a number average molecular weight (Mn) of at least 300 g/mole. Preferably, greater than 90 or 94 or 96% of the polyolefin comprises terminal vinyl groups; or within the range of from 50 or 60 wt % to 70 or 80 or 90 or 95 or 98 or 99%. As described above, the vinyl terminated polyolefins preferably have a Mn value of at least 200 or 400 or 1000 or 5000 or 20,000 g/mole, or within the range of from 200 or 400 or 500 g/mole to 20,000 or 30,000 or 40,000 or 50,000 or 100,000 or 200,000 or 300,000 g/mole. The vinyl terminated polyolefins preferably have a weight average molecular weight (Mw) value of at least 500 or 800 or 1000 or 5000 or 20,000 g/mole, or within the range of from 500 or 800 or 1000 or 2000 g/mole to 6,000 or 10,000 or 12,000 or 20,000 or 30,000 or 40,000 or 50,000 or 100,000 or 200,000 or 300,000 g/mole. Preferably, the VTP useful herein is amorphous polypropylene, and desirably has a glass transition temperature (Tg) of less than 10 or 5 or 0° C., more preferably less than −10° C.; or within the range of from 0 or −5 or −10° C. to −30 or −40 or −50° C. or as described herein. The VTPs are preferably linear, meaning that there is no polymeric or oligomeric branching from the polymer backbone, or described quantitatively, having a branching index “g” (or g′(vis avg)) of at least 0.90 or 0.96 or 0.97 or 0.98, wherein the “branching index” is well known in the art and measurable by published means, and the value of such branching index referred to herein is within 10 or 20% of the value as measured by any common method of measuring the branching index for polyolefins as is known in the art such as in US 2013-0090433.
A particularly preferred VTP is one wherein the vinyl terminated polyolefin is a compound or mixture of compounds represented by the formula (V):
Figure US09657116-20170523-C00008
wherein each R is selected from hydrogen and C1 to C4 or C10 alkyls; and n is an integer from 2 or 4 or 10 or 20 to 50 or 100 or 200 or 500 or 800.
Inventive Process
Thus, disclosed herein is a method of functionalizing a vinyl terminated polyolefin, the method comprising, or consisting essentially of, combining a VTP and a α,β-unsaturated carbonyl compound at a temperature of at least 150 or 160 or 180 or 200 or 220 or 240 or 250° C. and a pressure of at least 14 or 20 or 50 or 100 or 200 or 300 or 400 psi, forming a functionalized polyolefin. More preferably, the reaction is conducted at a temperature within the range of from 190 or 200 or 220° C. to 260 or 280 or 300 or 320° C. Also, the preferred pressure range may be within the range from 80 or 100 or 120 psi to 300 or 350 or 400 or 500 psi. By “consisting essentially of” what is meant is that no other major reactants are present to effect the identity of the final functionalized polyolefin product to no more than 3 wt % of the total product.
Preferably, α,β-unsaturated carbonyl compound is an unsaturated anhydride. Even more preferably, the α,β-unsaturated carbonyl compound is a compound or mixture of compounds represented by one or more of the formulae (VI):
Figure US09657116-20170523-C00009
wherein each R is, independently, a hydrogen or a C1 to C10 or C20 alkyls (linear or branched), or mixture thereof. Most preferably, the α,β-unsaturated carbonyl compound is maleic anhydride or a C1 to C5 alkyl substituted version thereof, the structures not being limited to the cis- or trans-isomers thereof.
Desirably, the combining takes place using neat carbonyl compound and/or VTP, where the VTP may be molten if not a liquid at the desired reaction temperature. However, the carbonyl compound and VTP can be mixed with or without added solvent. Regardless, the carbonyl compound and VTP are mixed for a period within the range from a few minutes or 10 minutes or 30 minutes or 1 hour or 2 hours or 3 hours to 4 or 6 or 8 or 10 or 16 or 24 hours. Preferably, from 0.8 or 1.0 to 1.5 or 2.0 or 3.0 or 4.0 or 5.0 or 6.0 equivalents of the α,β-unsaturated carbonyl compound are added per equivalent of VTP. The combining preferably takes place in an inert atmosphere such as under nitrogen, most preferably to the exclusion of oxygen and/or water vapor. In any case, preferably, the combining takes place such that the resulting product of the combining, the functionalized polyolefin, has at least 0.3 or 0.5 or 0.6 or 0.8 or 0.9 or 1.0 or 1.1 functional groups per polyolefin chain; or within a range of from 0.3 or 0.5 or 0.8 or 0.9 to 1.3 or 1.4 or 1.6 or 1.8 or 2.0 or 2.5 or 3.0 functional groups per polyolefin chain.
It is possible to also combine with the VTP and carbonyl compound one or more Lewis Acids selected from the group consisting of titanium halides, titanium alkyls and alkoxys, tin halides, tin alkyls and alkoxys, aluminum halides, aluminum alkyls and alkoxys, boron halides, boron alkyls and alkoxys, zinc halides, and combinations thereof; preferably, wherein the Lewis Acid is selected from the group consisting of SnCl4, AlCl3, Me2AlCl, EtAlCl2, Et2AlCl, TiCl4, TiCl2(i-PrO)2, TiBr2(i-PrO)2, BF3 and mixtures thereof (where “Me” is methyl, “Et” is ethyl, and “i-Pr” is isopropyl). When a Lewis Acid is also combined, the temperature of combining is desirably lowered relative to when no Lewis Acid is combined, preferably within the range of from 0 or 10 or 20° C. to 20 or 30 or 50 or 60° C.
Described more particularly, the inventive functionalized polyolefin is preferably a compound or mixture of compounds represented by one or more of the formulae (VII):
Figure US09657116-20170523-C00010
wherein each R1 is, independently, selected from hydrogen or C1 to C4 or C10 alkyls; n is an integer from 2 or 4 or 10 or 20 or 50 or 100 or 200 or 500 or 800; and each X is, independently, a functional group derived from the α,β-unsaturated carbonyl compound. The most preferred functionalized polyolefin is a mono- or bis-succinic anhydride, or mixture thereof. The inventive functionalized polyolefin may be made by the inventive method described herein or any other desirable method.
The functionalized polyolefin may have any number of uses, such as fouling inhibitors or mitigators, or as additives in lubricant oils, or as additives in rubber/elastomeric compositions such as in tire treads to compatabilize the components therein.
The various descriptive elements and numerical ranges disclosed herein for the inventive method and polymer compositions can be combined with other descriptive elements and numerical ranges to describe the method and polymer compositions therefrom; further, for a given element, any upper numerical limit can be combined with any lower numerical limit described herein. The features of the invention are demonstrated in the following non-limiting examples.
EXAMPLES
Unless otherwise stated, Mn (GPC) was determined using the GPC-DRI method described below. Mn, Mw, and Mz may be measured by using a Gel Permeation Chromatography (GPC) method using a High Temperature Size Exclusion Chromatograph (SEC, either from Waters Corporation or Polymer Laboratories), equipped with a differential refractive index detector (DRI). Molecular weight distribution (MWD) is Mw (GPC)/Mn (GPC). Experimental details, are described in T. Sun et al. in 34(19) MACROMOLECULES pp. 6812-6820 (2001) and references therein. Three Polymer Laboratories PLgel 10 mm Mixed-B columns are used. The nominal flow rate is 0.5 cm3/min and the nominal injection volume is 300 μL. The various transfer lines, columns and differential refractometer (the DRI detector) are contained in an oven maintained at 135° C. Solvent for the SEC experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4 trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. The TCB is then degassed with an online degasser before entering the SEC. Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160° C. with continuous agitation for about 2 hours. All quantities are measured gravimetrically. The TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/mL at 25° C. and 1.324 g/mL at 135° C. The injection concentration is from 1.0 to 2.0 mg/mL, with lower concentrations being used for higher molecular weight samples. Prior to running each sample the DRI detector and the injector are purged. Flow rate in the apparatus is then increased to 0.5 mL/minute, and the DRI is allowed to stabilize for 8 to 9 hours before injecting the first sample. The concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, IDRI, using the following equation:
c=K DRI I DRI/(dn/dc)
where KDRI is a constant determined by calibrating the DRI, and (dn/dc) is the refractive index increment for the system. The refractive index, n=1.500 for TCB at 135° C. and λ=690 nm. For purposes of this invention and the claims thereto, (dn/dc)=0.104 for propylene polymers and ethylene polymers, and 0.1 otherwise. Units of parameters used throughout this description of the SEC method are: concentration is expressed in g/cm3, molecular weight is expressed in g/mol, and intrinsic viscosity is expressed in dL/g.
Example 1. Maleation of Commercial Highly Reactive Polyisobutylene (HR-PIB)
To a two-neck 500 ml round-bottomed flask equipped with a N2 inlet and a N2 outlet was added highly reactive polyisobutylene (HR-PIB, TPC 5 from Texas Petrochemicals) (Mn 750 g/mol, 75 g, 100.00 mmol) followed by maleic anhydride (15.69 g, 160.00 mmol, 1.60 equiv) at room temperature (hereinafter 25° C.). The mixture was flushed with nitrogen for 10 min at room temperature and the mixture was heated to 190° C. (oil bath) for 7.25 hours under a nitrogen atmosphere and the mixture was allowed to cool to room temperature. The mixture was cooled to room temperature, diluted with hexanes (200 ml), filtered and concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95-100° C. under high vacuum for 4 fours to afford a light brown viscous oil as product (83.56 g). Elemental analyses for this polyisobutylene succinic anhydride found C: 81.30%, H: 13.36%. The oxygen content of this material is estimated to be about 5.34 wt % by difference. The anhydride content of this polymer material is estimated to be about 1.113 mmol/g. Based on the molecular weight of polymer starting material, there is about 1.11 succinic anhydride functionality per polymer chain.
Example 2. Maleation of Vinyl-Terminated Atactic Polypropylene
To a two-neck 500 ml round-bottomed flask equipped with a N2 inlet and a N2 outlet was added vinyl-terminated atactic polypropylene (GPC Mw 5646, Mn 1474, 1H NMR Mn 1190.19 g/mol, 75.00 g, 63.02 mmol) followed by maleic anhydride (15.45 g, 157.56 mmol) at room temperature. The mixture was flushed with nitrogen for 10 min at room temperature and the mixture was heated to 190° C. (oil bath) for 63.5 hours under a nitrogen atmosphere. Additional maleic anhydride (3.10 g, 31.61 mmol) was added to the mixture that had been cooled to about 120° C. and heating was continued at 190° C. (oil bath) for an additional 17 hours under a nitrogen atmosphere. The mixture was cooled to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95-100° C. under high vacuum to afford a light brown viscous oily product (85.70 g). GPC Mw 4020, Mn 1413. Elemental analyses for this polypropylene succinic anhydride found C: 80.79%, H: 12.51%. The oxygen content of this material is estimated to be about 6.70 wt % by difference. The anhydride content of this polymer material is estimated to be about 1.396 mmol/g. Based on the molecular weight of polymer starting material, there is about 1.93 succinic anhydride functionality per polymer chain.
Example 3. Maleation of Vinyl-Terminated Atactic Polypropylene
To a two-neck 500 ml round-bottomed flask equipped with a N2 inlet and a N2 outlet was added vinyl-terminated PP (Mn 2264.48 g/mol, 175.00 g, 77.28 mmol) followed by maleic anhydride (22.74 g, 231.90 mmol, 3.0 equiv) at room temperature. The mixture was flushed with nitrogen for 10 min at room temperature and mixture was heated to 190° C. (oil bath) for 70.75 hours under a nitrogen atmosphere. The mixture was allowed to cool to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95-100° C. under high vacuum for 5 hours to afford a light brown viscous oil as product (182.2 g). Elemental analyses for this polyisobutylene succinic anhydride found C: 83.50%, H: 13.68%. The oxygen content of this material is estimated to be about 2.82 wt % by difference. The anhydride content of this polymer material is estimated to be about 0.588 mmol/g. Based on the molecular weight of polymer starting material, there is about 1.41 succinic anhydride functionality per polymer chain.
Example 4. Maleation of Vinyl-Terminated Propylene/1-Hexene Copolymer
To a two-neck 500 ml round-bottomed flask equipped with a N2 inlet and a N2 outlet was added vinyl-terminated C3/C6 copolymer (Mn 1668.96 g/mol, 150 g, 89.88 mmol) followed by maleic anhydride (24.24 g, 247.20 mmol, 2.75 equiv) at room temperature. The mixture was flushed with nitrogen for 10 min at room temperature and mixture was heated to 190° C. (oil bath) for 99 hours under a nitrogen atmosphere. The mixture was allowed to cool to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator. The mixture was heated at 95-100° C. under high vacuum for 5 hours to afford a light brown viscous oil as product (165.4 g). Elemental analyses for this polyisobutylene succinic anhydride found C: 82.80%, H: 13.21%. The oxygen content of this material is estimated to be about 3.99 wt % by difference. The anhydride content of this polymer material is estimated to be about 0.831 mmol/g. Based on the molecular weight of polymer starting material, there is about 1.51 succinic anhydride functionality per polymer chain.
Example 5. Maleation of Vinyl-Terminated Propylene/1-Butene Copolymer
To a two-neck 250 ml round-bottomed flask equipped with a N2 inlet and a N2 outlet was added vinyl-terminated C3/C4 copolymer (Mn 1062.16 g/mol, 50 g, 47.07 mmol) followed by maleic anhydride (9.23 g, 94.13 mmol, 2.0 equiv) at room temperature and mixture was heated to 190° C. (oil bath) for 84.5 hours under a nitrogen atmosphere. The mixture was allowed to cool to room temperature, diluted with hexanes, filtered and concentrated on a rotary evaporator. The mixture was heated at 95-100° C. under high vacuum for 5 hours to afford a light brown viscous oil as product (54.97 g). Elemental analyses for this polyisobutylene succinic anhydride found C: 81.76%, H: 13.09%. The oxygen content of this material is estimated to be about 5.15 wt % by difference. The anhydride content of this polymer material is estimated to be about 1.073 mmol/g. Based on the molecular weight of polymer starting material, there is about 1.27 succinic anhydride functionality per polymer chain.
Example 6. Maleation of Vinyl-Terminated Atactic Polypropylene
To a 300 ml stainless steel autoclave equipped with a mechanical stirrer and N2 inlet and a N2 outlet was added vinyl-terminated PP (Mn 1015.76 g/mol, 50 g, 49.22 mmol) followed by maleic anhydride (9.66 g, 98.51 mmol, 2.00 equiv) at room temperature. The mixture was stirred and flushed three times with nitrogen at room temperature and pressurized to about 80-85 psi. The mixture was heated to 200° C. for 2 hr at about 125-130 psi and allowed to cool to room temperature. The pressure was released slowly and the autoclave was opened. The mixture was diluted with hexanes, filtered under house vacuum and the filtrate was concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95° C. under high vacuum to afford a light yellow viscous oily product (49.4 g). Elemental analyses for this polypropylene succinic anhydride found C: 84.87%, H: 14.16%. The oxygen content of this material is estimated to be about 0.97 wt % by difference. The anhydride content of this copolymer material is estimated to be about 0.202 mmol/g. Based on the molecular weight of polymer starting material, there is about 0.21 succinic anhydride functionality per polymer chain.
Example 7. Maleation of Vinyl-Terminated Atactic Polypropylene
To a 300 ml stainless steel autoclave equipped with a mechanical stirrer and N2 inlet and a N2 outlet was added vinyl-terminated PP (Mn 1015.76 g/mol, 50 g, 49.22 mmol) followed by maleic anhydride (9.66 g, 98.51 mmol, 2.00 equiv) at room temperature. The mixture was stirred and flushed three times with nitrogen at room temperature and pressurized to about 80-85 psi. The mixture was heated to 225° C. for 2 hr at about 125-130 psi and allowed to cool to room temperature. The pressure was released slowly and autoclave was opened. The mixture was diluted with hexanes, filtered under house vacuum and the filtrate was concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95° C. under high vacuum to afford a light brown viscous oily product (51.12 g). Elemental analyses for this polypropylene succinic anhydride found C: 83.26%, H: 13.43%. The oxygen content of this material is estimated to be about 3.31 wt % by difference. The anhydride content of this copolymer material is estimated to be about 0.690 mmol/g. Based on the molecular weight of polymer starting material, there is about 0.751 succinic anhydride functionality per polymer chain.
Example 8. Maleation of Vinyl-Terminated Atactic Polypropylene
To a 300 ml stainless steel autoclave equipped with a mechanical stirrer and N2 inlet and a N2 outlet was added vinyl-terminated PP (Mn 1015.76 g/mol, 90 g, 88.60 mmol) followed by maleic anhydride (17.38 g, 177.24 mmol, 2.0 equiv) at room temperature. The mixture was stirred and flushed three times with nitrogen at room temperature and pressurized to about 80-85 psi. The mixture was heated to 250° C. for 3 hr about 125-130 psi and allowed to cool to room temperature. The pressure was released slowly and autoclave was opened. The mixture was diluted with hexanes, filtered under house vacuum and the filtrate was concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95° C. under high vacuum to afford a light brown viscous oily product. Elemental analyses for this polypropylene succinic anhydride found C: 81.24%, H: 12.84%. The oxygen content of this material is estimated to be about 5.92 wt % by difference. The anhydride content of this copolymer material is estimated to be about 1.233 mmol/g. Based on the molecular weight of polymer starting material, there is about 1.425 succinic anhydride functionality per polymer chain.
Example 9. Maleation of Vinyl-Terminated Atactic Polypropylene
To a 300 ml stainless steel autoclave equipped with a mechanical stirrer and N2 inlet and a N2 outlet was added vinyl-terminated PP (Mn 1865.85 g/mol, 90 g, 48.24 mmol) followed by maleic anhydride (18.92 g, 192.94 mmol, 4.0 equiv) at room temperature. The mixture was stirred and flushed three times with nitrogen at room temperature and pressurized to 300 psi. The mixture was heated to 250° C. for 3 hr and allowed to cool to room temperature. The pressure was released slowly and autoclave was opened. The mixture was diluted with hexanes, filtered under house vacuum and the filtrate was concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95° C. under high vacuum to afford a light brown viscous oily product (93.3 g). Elemental analyses for this polypropylene succinic anhydride found C: 82.41%, H: 13.31%. The oxygen content of this material is estimated to be about 4.28 wt % by difference. The anhydride content of this copolymer material is estimated to be about 0.892 mmol/g. Based on the molecular weight of polymer starting material, there is about 1.823 succinic anhydride functionality per polymer chain.
Example 10. Maleation of Vinyl-Terminated Atactic Polypropylene with Low Polydispersity (Mw/Mn=1.20)
To a 300 ml stainless steel autoclave equipped with a mechanical stirrer and N2 inlet and a N2 outlet was added vinyl-terminated PP (Mn 1312.25 g/mol, 50 g, 38.10 mmol) followed by maleic anhydride (7.47 g, 76.18 mmol, 2.00 equiv) at room temperature. The mixture was stirred and flushed three times with nitrogen at room temperature and pressurized to about 80-85 psi. The mixture was heated to 250° C. for 3 hr at about 125-130 psi and allowed to cool to room temperature. The pressure was released slowly and autoclave was opened. The mixture was diluted with hexanes, filtered under house vacuum and the filtrate was concentrated on a rotary evaporator. Excess maleic anhydride was removed by heating at 95° C. under high vacuum to afford a light brown viscous oily product (53.1 g). Elemental analyses for this polypropylene succinic anhydride found C: 82.67%, H: 13.58%. The oxygen content of this material is estimated to be about 3.75 wt % by difference. The anhydride content of this copolymer material is estimated to be about 0.781 mmol/g. Based on the molecular weight of polymer starting material, there is about 1.110 succinic anhydride functionality per polymer chain. The polydispersity of the PP-SA material is 1.27 as determined by GPC (THF, 40° C.).
The inventors have found that the maleation of aPP (Mn of about 1000 g/mol) at elevated temperature gave much improved conversion of the vinyl group, providing a material with average 0.75 succinic anhydride functionality per polymer after 2 hours at 225° C. when 2 equivalents of MA was used in autoclave (Example 7). When the reaction temperature was further raised to 250° C. and the reaction time extended to 3 hours, the functionalization has increased to 1.42 succinic anhydride functionality per polymer (Example 8). Further exemplification of the benefits of employing an elevated temperature in promoting the maleation of vinyl double bond are evident by comparing Example 9 or 10 (reaction time about 3 hours at 250° C. in autoclave) with Examples 2, 3, 4, 5 (reaction time between 70 to 99 hours at 190° C. in glassware).
Now, having described the various features of the inventive method of making a functionalized polyolefin and the functionalized polymer therefrom, disclosed here in numbered paragraphs is:
P1. A functionalized polyolefin comprising a compound or mixture of compounds represented by one or more of the following formulae:
Figure US09657116-20170523-C00011
wherein each R1 is, independently, selected from hydrogen or C1 to C4 or C10 alkyls; n is an integer from 2 or 4 or 10 or 20 to 50 or 100 or 200 or 500 or 800; and each X is, independently, a functional group derived from the α,β-unsaturated carbonyl compound.
P2. A method of functionalizing a vinyl terminated polyolefin, the method comprising (or consisting essentially of) combining a vinyl terminated polyolefin and a α,β-unsaturated carbonyl compound at a temperature of at least 150 or 160 or 180 or 200 or 220 or 240 or 250° C. and a pressure of at least 14 or 20 or 50 or 100 or 200 or 300 or 400 psi, forming a functionalized polyolefin, preferably the functionalized polyolefin of paragraph 1.
P3. The method of numbered paragraph 2, wherein the α,β-unsaturated carbonyl compound is an unsaturated anhydride.
P4. The method of numbered paragraphs 2 or 3, wherein the α,β-unsaturated carbonyl compound is compound or mixture of compounds represented by one or more of the following formulae:
Figure US09657116-20170523-C00012
wherein each R is, independently, a hydrogen, a C1 to C10 or C20 alkyls (linear or branched), or mixture thereof; preferably, the α,β-unsaturated carbonyl compound is maleic anhydride, the structures not being limited to the cis- or trans-isomers thereof.
P5. The method of any one of the previous numbered paragraphs, wherein the vinyl terminated polyolefin is compound or mixture of compounds represented the formula:
Figure US09657116-20170523-C00013
wherein R is selected from hydrogen and C1 to C4 or C10 alkyls; and n is an integer from 2 or 4 or 10 or 20 to 50 or 100 or 200 or 500 or 800.
P6. The method of any one of the previous numbered paragraphs, wherein the vinyl terminated polyolefin has a number average molecular weight (Mn) within the range from 200 or 300 or 400 or 500 g/mole to 1000 or 2000 or 4000 or 10,000 or 15,000 or 20,000 or 30,000 g/mole.
P7. The method of any one of the previous numbered paragraphs, wherein the functionalized polyolefin has at least 0.3 or 0.5 or 0.6 or 0.8 or 0.9 or 1.0 or 1.1 functional groups per polyolefin chain; or within a range of from 0.3 or 0.5 or 0.8 or 0.9 to 1.3 or 1.4 or 1.6 or 1.8 or 2.0 or 2.5 or 3.0 functional groups per polyolefin chain.
P8. The method of any one of the previous numbered paragraphs, wherein the combining takes place in a period within the range from a few minutes or 10 minutes or 30 minutes or 1 hour or 2 hours or 3 hours to 4 or 6 or 8 or 10 or 16 or 24 hours.
P9. The method of any one of the previous numbered paragraphs, wherein the combining takes place in the presence of a Lewis Acid selected from the group consisting of titanium halides, titanium alkyls and alkoxys, tin halides, tin alkyls and alkoxys, aluminum halides, aluminum alkyls and alkoxys, boron halides, boron alkyls and alkoxys, zinc halides, and combinations thereof; more preferably, wherein the Lewis Acid is selected from the group consisting of SnCl4, AlCl3, Me2AlCl, EtAlCl2, Et2AlCl, TiCl4, TiCl2(i-PrO)2, TiBr2(i-PrO)2, BF3 and mixtures thereof (where “Me” is methyl, “Et” is ethyl, and “i-Pr” is isopropyl).
P10. The method of numbered paragraph 9, wherein the temperature of combining is within the range of from 0 or 10 or 20° C. to 20 or 30 or 50 or 60° C.
P11. The method of any one of the previous numbered paragraphs, wherein the functionalized polyolefin is a compound or mixture of compounds represented the one or more of the following formulae:
Figure US09657116-20170523-C00014
wherein each R1 is, independently, selected from hydrogen or C1 to C4 or C10 alkyls; n is an integer from 2 or 4 or 10 or 20 or 50 or 100 or 200 or 500 or 800; and each X is, independently, a functional group derived from the α,β-unsaturated carbonyl compound.
P12. The method of any one of the previous numbered paragraphs, wherein the combining takes place in an inert atmosphere.
P13. The method of any one of the previous numbered paragraphs, wherein from 0.8 or 1.0 to 1.5 or 2.0 or 3.0 or 4.0 or 5.0 or 6.0 equivalents of the α,β-unsaturated carbonyl compound are added per equivalent of VTP.
P14. A functionalized polyolefin made by the method of any one of the previous numbered paragraphs.
Also described is the use of a vinyl terminated polyolefin in a reaction with at least one α,β-unsaturated carbonyl compound as these components are described herein. Also described is the use of the inventive functionalized polyolefin as a fouling mitigator, or compatabilizer in elastomeric or lubricant compositions.
All patents and patent applications, test procedures and other documents cited herein are fully incorporated by reference to the extent such disclosure is not inconsistent with this invention and for all jurisdictions in which such incorporation is permitted.

Claims (9)

The invention claimed is:
1. A method of functionalizing a vinyl terminated polyolefin, the method comprising combining a vinyl terminated polyolefin and a α,β-unsaturated carbonyl compound at a temperature of at least 150° C. and a pressure of at least 14 psi, forming the functionalized polyolefin,
wherein the α,β-unsaturated carbonyl compound is compound or mixture of compounds represented by one or more of the following formulae:
Figure US09657116-20170523-C00015
wherein the functionalized polyolefin is a compound or mixture of compounds represented the one or more of the following formulae:
Figure US09657116-20170523-C00016
wherein each R1 is, independently, selected from hydrogen or C1 to C10 alkyls; n is an integer from 2 to 800; and each X is, independently, a functional group derived from the α,β-unsaturated carbonyl compound.
2. The method of claim 1, wherein the vinyl terminated polyolefin is compound or mixture of compounds represented the formula:
Figure US09657116-20170523-C00017
wherein R is selected from hydrogen and C1 to C4 or C10 alkyls; and n is an integer from 2 or to 800.
3. The method of claim 1, wherein the vinyl terminated polyolefin has a number average molecular weight (Mn) within the range from 200 g/mole to 30,000 g/mole.
4. The method of claim 1, wherein the functionalized polyolefin has at least 0.3 functional groups per polyolefin chain.
5. The method of claim 1, wherein the combining takes place in a period within the range from a few minutes or 10 minutes to 24 hours.
6. The method of claim 1, wherein the combining takes place in the presence of a Lewis Acid selected from the group consisting of titanium halides, titanium alkyls and alkoxys, tin halides, tin alkyls and alkoxys, aluminum halides, aluminum alkyls and alkoxys, boron halides, boron alkyls and alkoxys, zinc halides, and combinations thereof.
7. The method of claim 6, wherein the temperature of combining is within the range of from 0° C. to 60° C.
8. The method of claim 1, wherein the combining takes place in an inert atmosphere.
9. The method of claim 1, wherein from 0.8 to 6.0 equivalents of the α,β-unsaturated carbonyl compound are added per equivalent of VTP.
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